Water-soluble azo dyestuffs containing reactive groups



United States Patent Ofiice 3,035,043 Patented May 15, 1962 3,035,043 WATER-SGLUBLE AZO DYESTUFFS CONTAlNlNG REACTIVE GROUPS Jakob Benz, Muenchenstein, and Lukas Schneider and Hans Siegrist, Basel, Switzerland, assignors to Sandoz Ltd., Basel, Switzerland, a Swiss firm No Drawing. Filed Dec. 22, 1958, Ser. No. 781,910 Claims priority, application Switzerland Dec. 23, 1957 6 Claims. (Cl. 260-152) This invention relates to water-soluble azo dyestuifs which contain at least once the reactive group The process for producing the said dyestufis consists in reacting 1 mole of a water-soluble organic azo dyestuif or an organic compound capable of azo dyestuif formation, the said dyestufi or compound containing at least one splittable atom or splittable atom grouping, with at least 1 mole of ethylene imine, the reaction product being subsequently converted into the azo dyestuff by suitable methods if necessary. The starting materials must be so chosen that the end products contain the number of water-solubilizing groups which is necessary for the intended application.

Examples of splittable atoms or atom groupings which -=may be employed in the process are halogen atoms and aryloxy groups. The halogen atoms are combined with the organic compound or the azo dyestufi, preferably as acid chlorides or acid fluorides, the splittable aryloxy groups are combined with the azo dyestuif or the organic compound in the form of carbamic acid esters. These esters react with ethylene imine in such a Way that the aryloxy group is split off and replaced by ethylene imine to give an asymmetrical urea of the formula The organic compounds or azo dyestuffs used as starting materials are reacted with ethylene imine, preferably in aqueous medium. The reaction can also be conducted in an organic solvent or a mixture of organic solvent or solvents and water, this type of medium being especially suitable for reacting intermediate products that are poorly soluble or insoluble in water.

Organic solvents suitable for this purpose are alcohols, acetone, benzene, chlorobenzene, toluene, etc.

The ethylene imine can be employed in concentrated form, as an aqueous solution, or in solution in an organic solvent. Alcohols, acetone, benzene, chlorobenzene and toluene are suitable solvents.

Since the ethylene imine ring must remain intact for the dyeing process, i.e. the chemical reaction between the reactive groups of the dyestuft' and the fiber the condensation, diazotization and coupling reactions are effected, under conditions as mild as possible e.g. at a temperature between and 40 C. and in the pH range of 5.0 to 10.0.

When the reactants are an acid halide and ethylene imine, an equivalent amount of hydrogen halide is formed. To neutralize this acid, an acid-binding agent is added to the reaction solution either at the start or in the course of the reaction. Suitable agents are, e.g., sodium or potassium carbonate, bicarbonate or hydroxide, tertiary bases such as dimethylaminobenzene, pyridine or quinoline.

Of the organic compounds which contain an ethylene imine group and are capable of azo dyestutf formation, preference is given to those which contain a diazotizable amino group and on diazotization can be coupled, or those which contain a carbon atom capable of azo coupling and can be reacted with diazo compounds. Naturally, the organic starting compounds themselves may contain azo groups.

In order to confer suflicient water-solubility on the new dyestuffs, the starting products as defined above must be chosen so as to ensure that the necessary number of watersolubilizing groups is present.

The new dyestuffs are suitable for dyeing, padding and printing fibers of vegetable and animal origin, fibers of regenerated cellulose, casein fibers, animalized cellulosic fibers, synthetic polyamide fibers, mixtures of these fibers, and leather.

If necessary the dyeings are subjected to an alkaline aftertreatment at moderate or high temperature and then soaped. They possess good fastness to light, washing, water, milling and perspiration.

The dyeings and prints produced with the new dyestuffs are especially valuable because the dyestuffs form a stable chemical linkage with the fiber molecule and therefore as a rule possess outstanding Wet fastness properties. If the total amount of dyestufi applied does not participate in the chemical reaction with the fiber, the unreacted proportion can be removed by suitable aftertreatments such as washing and/or soaping. For this purpose synthetic detergents can be used in addition to the normal washing agents, e.g. alkylarylsulfonates, sodium lauryl sulfate, sodium lauryl-polyglycol ether sulfates, monoand dialkylphenolpolyglycol ethers.

After application by dyeing, padding or printing methods the dyestuffs can be fixed in the same bath or in a fresh bath, if necessary after intermediate drying. If a fresh bath is used it is advisable to carry out fixation in the presence of Water-soluble salts, e.g. sodium sulfate, in order to prevent partial redissolving of the dyestuif in the bath. The reaction of the dyestuff radical with the fiber takes place at high temperature, e.g. under the conditions of heat setting. The operation can be accelerated or carried out at lower temperatures when agents of acid or alkaline reaction are added to the dyebath or aftertreating bath as catalysts.

The optimum conditions for the application of the dyestuifs can vary widely according to the type of fiber. In dyeing, padding and printing of animal fibers and synthetic polyamide fibers it is preferable to apply the dyestufi or to fix it in an acid, neutral or weakly alkaline medium, e.g. in presence of acetic acid, formic acid, sulfuric acid, ammonium sulfate, lactic acid, oxalic acid, sodium acetate, sodium bicarbonate, sodium or potassium carbonate, sodium metaphosphate, trimethylamine, pyridine, quinoline, etc. Dyeing can also be carried out in presence of levelling agents, e.g. polyoxyethylated fatty amines or mixtures of the same with alkylpolyglycol ethers, in an acetic acid to neutral bath, with the addition at the end of dyeing of small 3 amounts of an agent of alkaline reaction, e.g. ammonia, sodium bicarbonate or sodium carbonate, or compounds which react alkaline on heating, e.g. hexamethylenetetramine or urea, until the bath gives a neutral or Weakly alkaline reaction. The dyed goods are then rinsed well and, if necessary, soured with a little acetic acid.

The dyeing, padding and printing of cellulosic fibers is carried out to best efiect in an alkaline medium, e.g. in presence of sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium meta-silicate, sodium borate, Water-glass, trisodium phosphate, ammonia, trimethylamine, quaternary bases such as tetra-alkyl ammonium compounds etc. to preclude reduction reactions during dyeing, padding or printing, it is often an advantage to add a mild oxidizing agent such as sodium 1-nitrobenzene-3-sulfonate. As a rule dyeings on cellulosic fibers also are fixed at high temperature. Some of the dyestufis can be applied in cold dyebaths when a sufiiciently strong alkali such as sodium or potassium hydroxide or trisodium phosphate is used. After fixation, the dyed, padded or printed material is thoroughly rinsed and soaped to remove the unfixed proportion of dyestuff.

In the following examples the parts and percentages are by weight and the temperatures in degrees centigrade.

EXAMPLE 1 54.1 parts of the dyestufi which is obtained by the coupling of diazotized 2-aminonaphthalene-4.8-disulfonic acid with 1-amino-3-methylbenzene and subsequent reaction of the formed aminomonoazo dyestuif with chloroformic acid phenyl ester, are dissolved in 600 parts of water at room temperature. 10 parts of ethylene imine are dropped into the solution, which is then stirred for 30 minutes. Subsequently the dyestuif formed is salted out; the crystalline precipitate is filtered off and dried.

The new dyestufi dyes cotton, wool, fibers of regenerated cellulose and synthetic polyamide fibers in yellow shades of good fastness to light and washing.

In Table 1 below are listed further azo dyestuffs containing reactive groups, which are obtainable by reacting their phenylurethane derivatives with ethylene imine by the procedure described in the foregoing example. In the table they are characterized by the diazo component and the coupling component of the aminoazo compound upon which they are based, the coupling conditions, and the shade of their dyeings on cotton.

Table 1 See footnote at end of table.

On completion of coupling the acetylamino group of the diazo component is saponified to the amino group 1n alkaline solution.

EXAMPLE 12 28.6 parts of 1-carboxy-2-hydroxynaphthalene-6-sultonic acid chloride are added in portions in the course of about 20 minutes to a well stirred ice-cold mixture of 40 parts of water, 10 parts of sodium bicarbonate and 8 parts of ethylene imine. Stirring is continued for 30 minutes at 03 to bring about complete solution, upon which the reaction mass is diluted with ice-water to parts by volume. 15 parts of sodium chloride are added, causing the 1-carboxy-2-hydroxy-naphthalene-6-sulfonic acid-ethylene imide formed to be precipitated. When filtered the precipitate is a white granular filter cake which is processed further in the moist state.

The moist filter cake, which is equivalent to 31.5 parts of the sodium salt of l-carboxy-2-hydroxynaphthalene-6- suifonic acid ethylene imide, is stirred into an ice-cold solution of 15 parts of anhydrous sodium carbonate in 400 parts of Water. To the suspension is added in 15 minutes at 03 with stirring an aqueous suspension of the diazo compound of 17.3 parts of 1-aminobenzene-3 sulfonic acid. After stirring for 1 hour at low tempera-' ture the new dyestuif is precipitated in crystalline form. It is filtered off, washed free of alkali, and dried in vacuo at 30.

The new dyestufi is an orange-colored powder which dyes Wool, cotton and fibers of regenerated cellulose in bright orange shades of good fastness to light and washing.

EXAMPLE 13 When the 17.3 parts of l-aminobenzene-3-sulfonic acid used as diazo component in Example 12 are replaced by 30.3 parts of 2-aminonaphthalene-4.S-disulfonic acid, or by 35.7 parts of 4-amino-l.1'-azobenzene-3.4'-disulfonic acid, dyestufis are obtained which possess equally good fastness properties and dye cotton in red-orange or red shades respectively.

EXAMPLE 14 55 parts of the monoazo dyestufi obtained by alkaline coupling of the diazo compound of 17.5 parts of l-aminobenzene-3-sulfonic acid fluoride with 40 parts of l-hydroxy-S-acetylaminonaphthalene-3.6-disulfonic acid, are dissolved in 500 parts of Water. 10 parts of ethylene imine are added at 15 with stirring. After stirring for 1 hour at 1520 the dyestufi formed is precipitated, filtered 01f and dried in vacuo at 50.

The new dyestufi dyes cotton and fibers of regenerated cellulose in red shades of good light and washing fastness.

The following Table 2 contains further azo dyestuffs containing reactive groups which can be produced in accordance with the foregoing example by reacting the sulfonic acid fluoride groups with ethylene imine. They are characterized by the diazo and coupling components, the coupling conditions and the shade of their dyeings on cotton.

Table 2 Table 3-Continued Ex. Coupling Coupling Shade on Ex. No. Diazo component Coupling component Shade on No. Diazo component conditions component cotton cotton 15..-. l-arninobenzene- Acid 2-amino-8-hy- Red. 27 l-amino-2-1nethyll-chloro-Sdrydroxy- Red.

3-sulfonic acid droxy'naphbenzene-fi-sulfonic napthalene-3.6 fluoride. thalene 3.6- acid ethyldisulfonic acid disulfonic acid. eneimide 16 l-amino-Z-rneth- Alkaline 1-phenyl-3-meth- Yellow. 29. do 2-hydroxynaphtha- Do.

ylbenzene-5- yl-5-pyrazleue-3.6-disuli0nic sulfonic acid olone-2.5- 1 acid fluoride. disulionic acid. 0 29 do Zhydroxynaphtha- Do. 17..-- 2 mols l-amino- First acid with 1 1 mol l-amino-S- Greenish lone-3.6.8-trisulfonic ben zeneA-sulmol diazo hydroxy-naphblue. acid ionic acid fluocompound, thalene3.6- 30 l-aminobenzcne-et- 1-amino-8-hydroxy-2- Greenish ride. then alkaline disulfonic acid. sulionic acid phenyl-azonaplithablue.

with 1 mol ethyleneimide lene3.6.4-trisuldiazo comionic acid pound. 31 -do 1 mol of the diazo Blue, gray.

compound of 4- amino-ll agid l coupler wi lmo EXAMPLE 18 oi1-amino-8hydroxynaphthalene 175 parts of l-annnobenzeneA-sulfomc acid fluoride 3.6-disulionic acid are dissolved in 40 parts of ethanol and added with stirring to a mixture of 6 parts of ethylene imine and 50 1 Azobenzenc-3.4'-disu1fonic acid. parts of water. At a temperature of 15-20 the pH value is maintmed at 9.0 by gradual addition of about parts EXAMPLE 32 of a 10% sodium hydroxide solution. Stirring is continned for 2 hours at 20-25, after which the precipitated 25 190 Parts of mercensed Cotton fabllc are Padded 111 a l-aminobenzenei-sulfonic acid ethylene imide is filtered off, washed with water until free of alkali, and dried in, a vacuum desiccator over calcium chloride.

20 parts of l-aminobenzene-4-sulfonic acid-ethylene imide are suspended in 400 parts of ice-cold water. 20 parts of hydrochloric acid are added dropwise at 0-2 with stirring, followed by a solution of 7 parts of sodium nitrite in 20 parts of water. The diazo solution thus formed is filtered free of minute impurities and added v.in portions to an ice-cold solution of 33 parts of 1(2.5-

dichloro-4'-su1fophenyl)-3-methyl-5-pyrazolone, 20 parts of sodium bicarbonate and 200 parts of water. The monoazo dyestufi formed is precipitated by the addition of sodium chloride, filtered ofi and washed free of alkali with a sodium chloride solution. It isdried in vacuo at 50 and then ground. A yellow dyestufi of good Water solubility is obtained which dyes cotton and fibers of regenerated cellulose in yellow shades of good fastness to light and washing.

Table 3 below gives details of further azo dyestufis containing an ethylene imine ring, which can be produced according to the procedure described in the above exampie. The dyestuffs are characterized in the table by the diazo and coupling components and the shade of their dyelngs on cotton.

Table 3 Ex. No. Diazo component Coupling component Shade on cotton 19 l-amino-Z-chloroben- 1-(2.5-dichlorc- Yellow zene-fi-sulfonic phenyll-3-methylacid-ethylcne- 5-pyrazolone-4- imide sulfonic acid 20 l-aminobenzene-- Q-acetylamino-i- Orange sulionic acid hydroxy-naphcthylene-imide thalene-lJ-disulionic acid 21 -do Q-w-sulloacetylamino Do.

fi-hydroxynnphthalene-7-sulionic acid 22 do 3-acctylamino-5- Scarlet.

. hydroxy-naphthnlene-7-sulionic acid 23 do l-hydroxynaph- Red.

tl1nlcnc-3.6disul ionic acid 24 do l-ncetylamino-S- Do.

hydroxy-naphthalene 3.6-disulionio acid 25 do l-phenyl-Ii-methyl-fi- Yellow pyrazolone 2.5- disulfonic acid 25 l-zunino-Z-methyl- 1-(2,5-dichloro- Do.

benzeneo-snlfonic phenyl)-3-rnethylacid ethyl- 5-pyrazolone-4'- eneimide sulfonic acid 2% aqueous neutral solution of the dyestufi of Example 14 at room temperature. The fabric is squeezed to give an increase of 100% on its dry weight and is then conveyed into a developing bath on the jig (liquor ratio 1:5) containing 300 grams per liter of sodium chloride and 10 milliliters per liter of sodium hydroxide solution of 66 Tw. It is treated in this bath for 40 minutes at -90 and subsequently rinsed well in cold water, soaped at the boil for 20 minutes with 5 grams per liter of soap, well rinsed, and dried. The bluish red dyeing obtained is fast to light and washing.

EXAMPLE 33 7 l K S OH NHn CE; CH2

I NOzS-N=N -N=N SO2N\I 0%, 01;,

E035 -SO3H 4. The dye of the formula CH, /CN SO3H I I NOzSON=NC/ I 1 s03];

o I G1 f SOzN I CH3 7 10 \CH2 5. The dye of the formula OH NH:

V 6. The dye of the formula 2. The dye of the formula Ho ('31 803E CH2 \C-NQSOQH 2 I NOzSO-N=NO I @-NN- \NHCON I g o1 CH2 CH3 H3 SOSH References Cited in the file of this patent UNITED STATES PATENTS 2,233,475 Dreyfus Mar. 4, 1941 The d Of the formula 2,819,259 Schmid et el. Ian. 7, 1958 ye 2,895,785 Alsberg et a1. July 21, 1959 S0311 OH FOREIGN PATENTS N:N 0 884,446 France Apr. 27, 1943 0111 OTHER REFERENCES 03 Wegmann: Textile-Praxis, October 1958, pages 1056 

1.A MEMBER FROM THE GROUP CONSISTING OF THE DYES OF THE FORMULAS 